Process for dyeing textile fibers



Patented Nov 28, 1944 PROCESS FOR DYEING TEXTILE FIBERS Chiles Emory Sparks and JosephFi-ancls Iaucius,

Wilmington, DeL, assignors to E1. du Pont'de Nemours & Company, WllmingtomDeh, a corporation of Delaware No Drawing, Application December 31 1942, Serial N- 470,836

Claims.

'I'hisinvention relates to an improved process It is an object of this invention to improve the afilnity of the fiber for the azotized polyaminophthalocyanine compound, whereby to obtain stronger dyeings on the fiber while using relativelyweak impregnation baths. It is a further object of this invention to provide an improved .method of procedure whereby the impregnation bath, which is generally an aqueous solution of the azotized polyamino-phthalocyanine compound, shall become substantially exhausted of color in the dyeing, thus increasing thegeneral economy of the process. Other and further important objects of this invention will appear as the description proceeds.

In this specification and in the claims below the term azotized is used as a generic term for the common expressions diazotized, tetrazotized and polydiazotized." In other words, it is intended to describe the state of a substance or the process wherein one or more amino groups have been converted into diazonium groups, the prefixes di-, tetraor polydibeing dropped off to avoid confusion.

In British Patent No. 535,935 is disclosed a process of dyeing textile materials by impregnating the same with an aqueous solution containing azotized tetra-amino-phthalocyanines, and then treating the fiber to develop the color on the fiber. Two modes of development are therein described. In one of these, the impregnated fiber is treated under conditions which result in decomposition of the diazoniu'm groups, producing on the fiber fast colors of the phthalocyanine series.

The condition generally involve heating in the presence of water or steam alone, in the presence of aliphatic alcohols, or in thepresence of aqueous solutions of substances which are not generally coupling components for the production of azo dyes. The resulting color on the fiber is therefore not an azo dye. In the other method, development is effected at moderate temperature, say 0 to 30 C., that is, a temperature less than that which would decompose the diazo groups, but the treatment bath contains an azoic coupling a the fiber.

lar fashion and a water-insoluble azo color of the phthalocyanine series is produced on the fiber.

According to latest developments in this field (which constitute subject matter or a patent application by James William Libby, Jr., serial No. 471,731), development on the fiber may alsobe achieved by reaction with coupling components which possess water-solubilizing groups; for instance, the naphthol-sulfonie acids, the aminonaphthol-sultonic acids, the aryl-pyrazoIone-carboxylic acids, the sulto-aryl-pyrazolones, and other similar components which are generally considered as outside the class of azoic coupling components; and there results on the fiber nevertheless a dyeing of satisfactory fastness qualities. In still another process, the developed dyeing on the fiber is further developed by treatment with metallizing agents which further modify or improve its iastness qualities or shade.

Again, according to copending application Serial No. 443,668 byg l. H. Haddock (Patent No.

2,349,090,, issued May 16, 1944)', it is possible to color fabric either by paddingit with an aqueous bath or by printing itwith a printing paste containing. a stabilized modification of an az otized polyamino-phthalocyanine, and then treating the fabric by various methods to develop the color on Several different modes of stabilization of the diazo group have been mentioned and discussed in said application, but the process of applying them to the fiber is essentially the process.

.tized polyamino-phthalocyanlnes for cellulosic fiber. As a result, strong dyeings are not obtaiiiable unless concentrated padding baths are employed, and the exhaustion of color in these baths is unsatisfactory. In the case of azotized copper-tetra-amino-phthalocyanine, for instance, when applied without the aid of the special pretreatment of this invention, a highly concentrated solution of the tetradiazonium compound must be used to get strong dyeings, and the exhaustion is poor.

component, whereby coupling takes place in reguu We have now round that the aflinity of textile fiber for azotized polyamino-phthalocyanines may be considerably increased, sometimes several fold, and that strong dyeings after the eventual development may be obtained, if the fabric is pretreated or mordanted, so to speak, with an aqueous bath containing a water-soluble heteropoly compound, or the acid or water-soluble salt-form of the heavy metal constituent of a heteropoly acid; in other words, vanadic, molybdie or tungstic acids and their salts. Our novel process of dyeing therefore comprises the steps ofimpregnating the textile material, for instance cotton, wool, cellulose acetate or nylon, with an aqueous bath containing heteropoly acids or derivatives thereof, entering the textile into a solution of an azotized amino-phthalocyanine, working the goods until the solution is well exhausted of its soluble azotized product, and finally fixing or developing the dyed textile with various agents or under various conditions, as hereinabove mentioned, to cause the diazonium groups to be decomposed, exchanged, reduced or coupled, yielding the desired shade ofdyeing. In this manner,

strengths many times greater than those of British Patent No. 535,935 are obtained; moreover, the azotized phthalocyanine can be exhausted from the dyebath.

Heteropoly compounds include those acids and salts which contain acid anhydrides of one or more elements combined with a hydrate or salt of the acid of another element. (Text Book of Inorganic Chemistry, edited by J. Newton Friend, vol. VII, part 111, page 163. Other definitions may be found in Text Book of Inorganic Chemistry by Fritz Ephraim; translated by Thorne, London, 1926, pages 405-415; also, Systematic Inorganic Chemistry by Caven and Lander, London, 1932, page 327.) The heteropoly acids generally contain the anhydride of a heavy metal from the th or 6th group of the periodic system, more especially vanadium, molybdenum or tungsten,

' and are typified further by the following examples which we have found useful for our invention: phospho-molybdic acid, phospho-tungstic acid, phospho-molybdo-tungstic acid, phosphovanadie acid, silico-tungstic acid, boro-tungstic acid, sili'co-molybdic acid and boro-molybdic acid. The acids or salts of the heavy metal constituent of the hetero-poly acid may be used also, for example sodium molybdate, sodium tungstate, tungstic acid, etc. These compounds may be applied to the textiles as free acids or as the alkali metal salts or as a mixture of free acids or a mixture of salts, as for example, a mixture of disodium hydrogen phosphate and sodium tun state or a'mixture of disodium hydrogen phosphate and sodium molybdate. The quantities of these agents in the pre-treatment bath may be varied within wide limits, for instance from 0.1 to 2.5 parts by weight per 100 parts by weight of textile material to be treated. v

As a further feature of our invention, the textile fiber may be further treated, prior to dyeing with the diazo compound, with agents adapted to fix the heteropoly acids on the fiber by lowering their solubility. i Suitable agents for this purpose are water-soluble ammonium salts, quaternary ammonium compounds and water-soluble guanidinederivatives, as typified by ammonium chloride, guanidine carbonate, cetyl pyridinium bromide, octadecyl pyridinium bromide, and betaureido-ethyl-pyridinium chloride. The amounts of these auxiliary agents used in this fixing treatfrom 0.1 to 1.5% based on the weight of the textile material treated.

As for the azotized polyamino-phthalocyanines to w ch our invention is applicable, these may be any of those hitherto mentioned in the art for this purpose. For instance, they may be derived from copper-tetra -(4) amino phthalocyanine, copper-tetra-(3) -,amino-phthalocyanine, coppertriamino phthalocyanine, copper d i a min 0 phthalocyanine and the corresponding polyamino derivatives of nickel-phthalocyanine, cobaltphthalocyanine or dihydrogen-phthalocyanine (metal-free phthalocyanine). The aminophthalocyanine is azotized in the usual manner with sodium nitrite and mineral acid, and the padded cloth is passed through the solution until the desired strength is attained or until the soluble diazonium compound is exhausted. Alternatively, an aqueous solution of a stabilized form of the polydiazonium phthalocyanine compound, for instance the zinc chloride double salt, may be employed as impregnation bath.

The development of the color on the fiber may beefiected in any one of the various methods aforementioned and may include for instance:

I. Treatments designed to decompose the diazonium groups, or to replace them by radicals which are not in the class of coupling components. Agents suitable for this purpose are: water, methyl alcohol, ethyl alcohol, ethylene glycol, diethylene glycol, ethylene-glycol-monomethyl-ether, sodium.- sulfide, pyridine, sodium carbonate, ammonia, potassium dichromate, so-' dium hypophosphite, potassium iodide, potassium bromide, cuprous chloride, sodium thiosuli'ate, and glucose, either at ordinary or raised temperatures.

II. Treatment with aqueous baths containing coupling components, for instance:

(a) Coupling compounds containing reactive methylene groups, such as the pyrazolones, aryl pyrazolones, 'aryl pyrazolone carboxylic acids, dimethyl-dihydro-resorcinol, acetyl acetone, acetoacet arylides, and barbituric acid;

(b) Ice colorcoupling components (so-called azoic coupling components), such as alphaand beta-naphthol, the naphthol-carboxylic acids, and the arylamides of 2,3-hydroxy-naphthoic acid;

(0) Various other coupling components, such as the phenols, carboxy-phenols, naphthol-sulfonic acids, naphthol-disulfonic acids, naphtholtrisulfonic acids, amino-naphthol-sulfonic acids,

amino-naphtho1-disulfonic acids, amino-naphthols, amino-naphthalene-sulfonic acids, hydroxy-quinolines, resorcin, .meta-phenylene-diamine; and

(d) Mixtures of any of the above.

A variety of shades may be obtained, as will be further shown by the following examples which are given to illustrate the invention without any intent to limitit. Parts mentioned are by weight.

Example 1 ment may likewise vary within wide limits; say, azotizing 1.8 parts of copper tetra-(4)-aminowhich is..'extremely fast to light,.washing and weathering is obtained.

If ethyl alcohol at 70 C., ethylene glycol at 100 1 C., or diethylene glycol at 100 C. is substituted for 'the boilingwater, a strong, bright blue dyeing. extremely fast to light, washing and weathering is obtained.

i i w -E:cample;,2; 3

Cotton sheeting (180) parts) is prepadded with a solution containing 3.9 parts sodium molybdate, 0.44 part disodium hydrogen phosphate and 6 parts concentrated hydrochloric acid in 500 parts water, and then passed through a wringer set so that 180 parts of solution are retained by the cloth. The sheeting is then passed through a solution containing 20 parts ammonium chloride in 400 parts water and then passed through the wringer so that 180 parts of solution are retained by the cloth. -The cloth is then impregnated with azotized tetramino-copper-phthalocyanine as in Example 1. The rinsed cloth is passed through a aqueous solution of 1-(4'-sulfo-phenyl) -3- methyl-5'-pyrazolone containing 5% sodium carbonate. There is obtained a green dyeing fast to light and washing.

In the place of 1-(4'-sulfo-phenyl)-3-methyl 5-pyrazolone. the following reagents may be substituted to give the shade listed below:

Reagent Shade 1 Z-naphthol Dull violet. 2 l-naphthol-4-sulionic acid Do. 3 Salicylic acid Blue green. 4 Ethyl-aceto-acetate. Bright green. 5 8-hydroxy-quinoline Grey. 6 l-amino-B-naph thol-Ztdisnlfonic acid. 7 l-naphthol-3,8-disnlfonic acid 8 l,S-dihydroxy-naphthalene-3,6-sullonic ac Do. 9 Acetyl acetone Bright green. 10 3-methyl 5-pyrazolone Green. ll l)imethyl-dihydro-resoreinol Bright green. 12 Barbitnric acid D0. 13 2.4-dihydroxy-quinoline Green. 14 Z-phenyl'amino-5-naphthoI-7 lie 0 a Grey. 15 1machthylamine-fi-sulfonic acid. Do. l6 Isophor'one Blue green.

17 Aceto-acet-p-phenctidide Green. 18 l-phenyi-B-meth yl-pyrazolone Do. 19 Anilide of 2-oxy-3-naphthoic ac Dull violet. 20 Resorcin Dull brown 21 mcta-Phenylene-diamine Brown. 22 Mixture of three parts l-(4-sulf0phenyl)-3- Black.

methyI-pyrazolone and one part m-phenylene-diarnine. Mixture of one part m-phenylenediarnine and '00.

one part ethyl aceto-acetate.

Example 3 Cloth prepadded and impregnated as in Ex- -,;,ample 1 is passed into a boiling 5% solution, of

" j sodium hypophosphite. A green-blue dyeing having excellent fastness to light, weathering. and washing is obtained.

If, in place of the boiling hypophosphite solution. there are used the following reagents, the tollowing shades are obtained: (Throughout this example and the next following. wherever solutions are named, unless otherwise specified, aqueous solutions are implied.)

Reagent Shade 1 57 potassium iodide solution Green. 2. 5% potassium bromide solution Do. 3 5% pyridine Do. 4 5% sodium sulfide solution... Do. 5 5% formaldehyde solution Blue green 6 5% formic acid solution Do. 7 Isoarnyl alcohol Blue. 8 2% potassium dichromate solution Dull green.

Example 5.

Cloth prepadded with 0.5% phosphomolybdic acidaccordingtothe procedure set forth in Example! is passed through an azotized solution 01 copper-tri- (4) -amino-phthalocyanine made from 1.2 parts copper tri-(4) -amino-phthalocyanine, 24 parts concentrated hydrochloric acid, 4 parts of 2-normal sodium nitrite, 300 parts of water, and ice to bring the temperature to 0-5 C. for one hour. The dyeing thus obtained is three times i as strong as one in which no prepadding agent is ill) used.

The dyed textile is then passed into a 5% solution of acetyl acetone to which 5% sodium carbonate was added. A bright yellow green dyeing having good washing and light fastness is obtained.

If in the above-example, acetyl acetone is replaced by other reagents, the following shades are obtained:

I Shade Reagent l 1-(4-sull'o-phenyl)-3-methyl-5-pyrazolo Green. 2 2-naphthol-3,6disulionicacid Dull violet. 3 2-amino-5-naphthol-7-sulfonic acid. Black-brown.

Example 6 shade blue is obtained.

Example 7 Five parts of cotton cloth were prepadded with 5 parts of a 1% solution of silico tungstic acid and the padded cloth was entered into a solution of azotized copper-tetra- (4) -amino-phthalocyanine. The dyeing showed approximately five times the strength over the dyeing of an unprepadded cloth treated in the same manner. The dyeing was treated with boiling water to give a green dyeing of excellent Iastness to light and washing. v

If in place of silico tungstic acid, sodium molybdate or a mixture of sodium molvbdate, sodium tungstate and sodium p osphate is used, a dyeing of similar properties is obtained.

Example 8 Viscose rayon is prepadded and impregnated as in Example 1. The impregnatedflber is passed into boiling water. A green dyeing fast to light and to washing is obtained. a

Example 9 Wool is prepadded and impregnated as in Example 1, and the treated material is steamed for five minutes. The resulting grjeen dyeing shows excellent fastness to light. i

In the above examples, in lieu of the freshly repared solutions of the azotized polyaminophthalocyanines, solutions of the corresponding zinc-chloride double-salts may be employed; and vice versa. Likewise, in any of the above examples where a metallizable azo dye is produced on the fiber, for instance an azo dye containing OH groups ortho to the azo groups or OH groups ortho to carboxylic acid groups, the fiber may be aftertreated with azo-dye metallizing agents, for instance, water-soluble salts of copper, nickel,

chromium or cobalt, a more fully described and claimed in copending applications of Libby and -WoodWard, Ser. No. 471,730, and of Rossander,

Libby and Woodward, Ser. No. 471,732;

Many other variation in details may be practiced with our invention, as will be readily apparent to those skilled in this art.

We claim:

1. In th process of padding textile material with a member of the group consisting of polydiazonium compounds of the phthalocyanine series and stabilized forms of said polydiazonium compounds, the improvement which consists of pretreating the fabric with a reagent selected from the group consisting of molybdic acid,

tungstic acid, vanadic acid, heteropoly acids dematerial is further treated with an agent selected from the group consisting of Water-soluble ammonium salts, quaternary ammonium compounds and water-soluble guanidine salts, prior to'treatment with said polydiazonium compounds.

4. A process for dyeing textile fiber, which comprises subjecting said fiber to a treatment which includes the step of impregnating said fiber with a compound selected from the group consisting of molybdic acid, tungstic acid, vanadic acid, heteropoly acids containing the nucleus of at least one of said acids, and water-soluble salts of any of the acids aforementioned, whereby to increase the afllnlty of the textile material for diazonium derivatives of phthalocyanine compounds: then impregnating said textile material with an azotiz'ed form of a polyamino-phthalocyanine compound; and thereafter subjecting the impregnated fiber to treatment adapted to develop the color on the fiber.

5. A process as in claim 4, wherein the treatment in the last mentioned step includes action upon the fiber with agents adapted to eliminate nitrogen from the diazonium groups on the fiber, whereby to produce a water-insoluble dyestufi on the fiber.

6. A process as in claim 4, wherein the treatment in the last mentioned step comprises treatment of the fiber with coupling components adapted to produce an azo dye On the fiber.

7. A process for dyeing textile fiber, which comprises subjecting said fiber to a treatment which includes the step of impregnating said fiber with a compound selected from the group consisting of molybdic acid, tungstic acid, vanadic acid, heteropoly acids containing the nucleus of at least one of said acids, and water-soluble salts of any of the acids aforementioned, whereby to increase the affinity of the textile material for diazonium derivatives of phthalocyanine compounds; then impregnating said textile material with an azotized form of copper-tetramino-phthalocyanine; and thereafter subjecting the impregnated fiber to treatment adapted to develop the color on the fiber.

8. A process as in claim 7, wherein the treatment in the last mentioned step consists of heating the impregnated fiber in contact with a liquid selected from the group consisting of water, aliphatic alcohols, and aqueous solutions of reagents which facilitate the elimination of nitrogen from the diazonium groups on the fiber.

9. A process as in claim 7, wherein the treatment in the last mentioned step consists of impregnating the fabric with reagents adapted to act as coupling components for the diazonium groups, whereby to develop an azo dyestufi 0n the fiber.

10. A process as in claim 7, wherein the fiber after the first mentioned impregnation and prior to impregnation with an azotized form of said color is further treated with a member of the 

